CS204582B1 - Process for preparing perfluor-4-methyl-2-pentendinitrile - Google Patents
Process for preparing perfluor-4-methyl-2-pentendinitrile Download PDFInfo
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- CS204582B1 CS204582B1 CS151479A CS151479A CS204582B1 CS 204582 B1 CS204582 B1 CS 204582B1 CS 151479 A CS151479 A CS 151479A CS 151479 A CS151479 A CS 151479A CS 204582 B1 CS204582 B1 CS 204582B1
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- methyl
- pentendinitrile
- perfluoro
- trifluoroacrylonitrile
- ether
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- 238000004519 manufacturing process Methods 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- CBCONFQTRQPRDE-UHFFFAOYSA-N 2,3,4-trifluoro-4-(trifluoromethyl)pent-2-enedinitrile Chemical compound N#CC(F)=C(F)C(F)(C#N)C(F)(F)F CBCONFQTRQPRDE-UHFFFAOYSA-N 0.000 claims description 14
- KDUAIKFAYXQCMF-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enenitrile Chemical compound FC(F)=C(F)C#N KDUAIKFAYXQCMF-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000006471 dimerization reaction Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 2
- DVMSVWIURPPRBC-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C(F)F DVMSVWIURPPRBC-UHFFFAOYSA-N 0.000 description 1
- LNUDZOHDUVPVPO-UHFFFAOYSA-N 3,3-difluoro-2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C(F)F)C(F)(F)F LNUDZOHDUVPVPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- IOIJXJFMFHVESQ-UHFFFAOYSA-M trimethyl(phenyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)C1=CC=CC=C1 IOIJXJFMFHVESQ-UHFFFAOYSA-M 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Vynález se týká způsobu přípravy perfluor-4-methyl-2-pentendinitrilu vzorceThe invention relates to a process for the preparation of perfluoro-4-methyl-2-pentendinitrile of the formula
NC — CF = CF—CF(CF3) —CN.NC - CF = CF - CF (CF 3 ) - CN.
Iontové dimerizace nenasycených fluorovaných látek jsou výhodnou syntetickou metodou, která umožňuje přípravu řady sloučenin, jež jsou jinými dosud známými postupy obtížně připravitelné nebo zcela nedostupné. Dimerizace probíhají u sloučenin s dvojnou vazbou, jež sestává z difluormethylové skupiny, a k níž jsou vázány elektronegativní skupiny, jako trifluomerthylová, alkoxykarbonylová a nitrilová, a dále elektronegativní substituenty jako fluor a chlor. Dimerizací esterů a nitrilů nenasycených perfluorkarboxylových kyselin, jako je kyselina perfluormethakrylová a trifluorakrylová, vznikají odpovídající bifunkční dimery. Příprava perfluor-4-methyl-2-pentendinitrilu dimerizací trifluor-akrylonitrilu nebyla dosud provedena.Ionic dimerizations of unsaturated fluorinated materials are a preferred synthetic method which allows the preparation of a number of compounds that are difficult to prepare or completely unavailable by other known methods. Dimerizations occur in compounds with a double bond consisting of a difluoromethyl group and to which electronegative groups such as trifluoromethyl, alkoxycarbonyl and nitrile are bonded, as well as electronegative substituents such as fluorine and chlorine. Dimerization of unsaturated perfluorocarboxylic acid esters and nitriles such as perfluoromethacrylic acid and trifluoroacrylic acid gives the corresponding bifunctional dimers. The preparation of perfluoro-4-methyl-2-pentendinitrile by dimerization of trifluoroacrylonitrile has not been carried out yet.
Dimerizace vysoce fluorovaných sloučenin, vyvolané působením fluoridů alkalických kovů, jsou iontovými reakcemi. Mechanismus dimerizací sestává z několika stupňů, které zahrnují adici karbaniontu a eliminaci fluoridového iontu, přitom reakční intermediáty mají povahu karbaniontů. Vhodná rozpouštědla velmi příznivě ovlivňují průběh dimerizací ze dvou důvodů. Za prvé se může uplatnit solvatace reakčních intermediátů, což má za následek snížení energetických bariér jednotlivých reakčních stupňů a tím rychlejší reakci; za druhé, reakce probíhající v rozpouštědle je možno snadno regulovat, zvláště pak reakce silně exotermní, mezi něž dimerizace náleží.The dimerization of the highly fluorinated compounds caused by the action of alkali metal fluorides are ionic reactions. The mechanism of dimerization consists of several steps, which include the addition of a carbanion and the elimination of the fluoride ion, the reaction intermediates being carbanion-like. Suitable solvents very favorably influence the course of dimerization for two reasons. Firstly, the solvation of the reaction intermediates may be applied, resulting in a reduction of the energy barriers of the individual reaction steps and thus a faster reaction; secondly, the reactions taking place in the solvent can be easily controlled, particularly the strongly exothermic reactions, which include dimerization.
Podle vynálezu se perfluor-4^methyl-2-pentendinitril vzorceAccording to the invention, perfluoro-4'-methyl-2-pentendinitrile of the formula
NC—CF = CF—CF(CF3) —CN připravuje tím, že se trifluorakrylonitril vzorce CF2 = CF—CN dimerizuje za přítomnosti katalyzátoru, tvořeného fluoridy alkalických kovů a/nebo hydrogenfluoridem draselným a/nebo kvartérními amoniovými fluoridy a/nebo terciárními aminy a/nebo triethanolaminem v prostředí organických rozpouštědel. Jako fluoridy alkalických kovů se použijí fluorid sodný a nebo fluorid draselný a nebo fluorid rubidný a nebo fluorid česný a nebo hydrogenfluorid draselný. Jako kvartérní amoniumfluoridy se použijí sloučeniny typu (R'R2 R3R4)N F-, kde R', R2, R3 a R4 jsou alkyly nebo aryly, např. trimethylfenylamoniumfluorid, trimethylbenzylamoniumfluorid, tetraethylamoniumfluorid. Jako terciální aminy se použijí sloučeniny typu R‘ř2R3N, kde R', R5 a R3 jsou alkyly například triethylamin, tributylamin, diethylmethylamin a podobně. Jako organické rozpouš204582 tédlo se použijí alifatické nebo cyklické ethery o počtu atomů uhlíku 3 až 10, výhodně 1,2-dimethoxyethan, diethylenglykoldimethylether a 1,3-dioxolan, a nebo amidy kyselin, výhodně dimethylformamid a hexamethyltriamidofosfát, a nebo sulfoxidy, výhodně dimethylsulfoxid, a nebo nitrolátky, výhodně nitrobenzen, a nebo sulfony, výhodně tetramethylensulfon, a nebo acetonitril a nebo kryptáty v roztoku diethylenglykoldimethyletheru a dibutyletheru, výhodně kryptát 18-crown-ether.NC - CF = CF - CF (CF 3 ) - CN is prepared by dimerizing the trifluoroacrylonitrile of formula CF 2 = CF - CN in the presence of a catalyst consisting of alkali metal fluorides and / or potassium hydrogen fluoride and / or quaternary ammonium fluorides and / or tertiary amines and / or triethanolamine in an organic solvent environment. As the alkali metal fluorides, sodium fluoride and / or potassium fluoride and / or rubidium fluoride or cesium fluoride or potassium hydrogen fluoride are used. As quaternary ammonium fluorides, compounds of the (R'R 2 R 3 R 4 ) N F- type are used, wherein R 1, R 2 , R 3 and R 4 are alkyl or aryl, e.g. trimethylphenylammonium fluoride, trimethylbenzylammonium fluoride, tetraethylammonium fluoride. As tertiary amines, compounds of the type R 1, R 2 R 3 N, where R ', R 5 and R 3 are alkyls such as triethylamine, tributylamine, diethylmethylamine and the like, are used. Aliphatic or cyclic ethers having a carbon number of 3 to 10, preferably 1,2-dimethoxyethane, diethylene glycol dimethyl ether and 1,3-dioxolane, and / or acid amides, preferably dimethylformamide and hexamethyltriamidophosphate, and / or sulfoxides, preferably dimethylsulfoxide, are used as the organic solvent. and or nitro compounds, preferably nitrobenzene, and or sulfones, preferably tetramethylene sulfone, and or acetonitrile and or cryptates in a solution of diethylene glycol dimethyl ether and dibutyl ether, preferably 18-crown-ether cryptate.
Perfluor-4-methyl-2-pentendinitril slouží jako meziprodukt při syntézách fluorovaných dusíkových sloučenin.Perfluoro-4-methyl-2-pentendinitrile serves as an intermediate in the synthesis of fluorinated nitrogen compounds.
Způsob podle vynálezu je dále popsán na několika příkladech provedení.The process according to the invention is further described in several exemplary embodiments.
Příklad 1Example 1
Směs 1 g fluoridu sodného, 5 g trifluorakrylonitrilu a 10 g 1,2-dimethoxyethanu byla třepána ve skleněné ampuli při teplotě 50 °C po dvě hodiny. Reakční směs byla zředěna 20 ml 1,1,2-trichlortrifluorethanu, olejovitá vrstva byla promyta vodou a vysušena bezvodým síranem hořečnatým. Po oddestilování rozpouštědla byl rektifikací získán perfluor-4-methyl-2-pentendinitril ve výtěžku 1,73 g, který byl jímán při 90—95 °C.A mixture of 1 g sodium fluoride, 5 g trifluoroacrylonitrile and 10 g 1,2-dimethoxyethane was shaken in a glass vial at 50 ° C for two hours. The reaction mixture was diluted with 20 mL of 1,1,2-trichlorotrifluoroethane, the oily layer was washed with water and dried over anhydrous magnesium sulfate. After distilling off the solvent, perfluoro-4-methyl-2-pentendinitrile was obtained by rectification in a yield of 1.73 g which was collected at 90-95 ° C.
Příklad 2Example 2
Směs 0,9 g fluoridu draselného, 0,3 g kryptátu 18-crown-6-etheru, 5 g trifluorakrylonitrilu a 10 ml diethylenglykoldimethyletheru byla třepána ve skleněné ampuli při teplotě 40—50 °C po 2 hodiny. Reakční směs pak byla zředěna 20 mlA mixture of 0.9 g of potassium fluoride, 0.3 g of 18-crown-6-ether cryptate, 5 g of trifluoroacrylonitrile and 10 ml of diethylene glycol dimethyl ether was shaken in a glass vial at 40-50 ° C for 2 hours. The reaction mixture was then diluted with 20 mL
1,1,2-trichloririfluorethanu, olejovitá vrstva promyta vodou a vysušena bezvodým síranem hořečnatým. Při rektifikaci byl jímán perfluor-4-methyl-2-pentendinitril ve výtěžku 1,36 g.Of 1,1,2-trichloririfluoroethane, the oily layer was washed with water and dried over anhydrous magnesium sulfate. Upon rectification, perfluoro-4-methyl-2-pentendinitrile was collected in a yield of 1.36 g.
Příklad 3Example 3
Směs 1,2 g hydrogenfluoridu draselného, 5 g trifluorakrylonitrilu a 10 ml dimethylsulfoxidu byla třepána ve skleněné ampuli při 50—60 °C po 3 hodiny. Reakční směs pak byla zředěna 20 ml l,l,2-trich|ortrifluorethanu, olejovitá vrstva byla promyta vodou a vysušena bezvodým síranem hořečnatým. Po oddestilování rozpouštědla byl rektifikaci získán perfluor-4-methyl-2-pentendinitril ve výtěžku 1,47 g.A mixture of 1.2 g of potassium hydrogen fluoride, 5 g of trifluoroacrylonitrile and 10 ml of dimethyl sulfoxide was shaken in a glass vial at 50-60 ° C for 3 hours. The reaction mixture was then diluted with 20 mL of 1,1,2-trichlorotrifluoroethane, the oily layer was washed with water and dried over anhydrous magnesium sulfate. After the solvent was distilled off, perfluoro-4-methyl-2-pentendinitrile was obtained in a yield of 1.47 g.
Příklad 4Example 4
Směs 1,3 g fluoridu česného, 5 g trifluorakrylonitrilu a 20 ml nitrobenzenu byla třepána ve skleněné ampuli při teplotě 70 °C po dvě hodiny. Reakční směs byla po odfiltrování pevné fáze destilována při tlaku 13,3 kPa a produkt byl zachycen v jímadle chlazeném směsí suchý led — — ethanol. Rektifikaci byl získán perfluor-4-methyl-2-pentendinitril ve výtěžku 2,51 g.A mixture of 1.3 g cesium fluoride, 5 g trifluoroacrylonitrile and 20 ml nitrobenzene was shaken in a glass vial at 70 ° C for two hours. The reaction mixture was distilled off at 13.3 kPa after the solid phase was filtered off and the product was collected in a dry ice-ethanol mixture receiver. Rectification gave perfluoro-4-methyl-2-pentendinitrile in a yield of 2.51 g.
Příklad 5Example 5
Směs 1 g fluoridu rubidného, 5 g trifluorakrylonitrilu a 20 ml acetonitrilu byla míchána při teplotě 15 °C po 4 hodiny. Reakční směs byla zředěna 20 ml diethyletheru, promyta vodou a vysušena bezvodým uhličitanem draselným. Po oddestilování rozpouštědla byl rektifikaci získán perfluor-4-methyl-2-pentendinitril ve výtěžku 0,96 g.A mixture of 1 g of rubidium fluoride, 5 g of trifluoroacrylonitrile and 20 ml of acetonitrile was stirred at 15 ° C for 4 hours. The reaction mixture was diluted with 20 mL of diethyl ether, washed with water and dried over anhydrous potassium carbonate. After distilling off the solvent, perfluoro-4-methyl-2-pentendinitrile was obtained in a yield of 0.96 g.
Příklad 6Example 6
Směs 1 g triethylaminu, 5 g trifluorakrylonitrilu a 20 ml acetonitrilu byla třepána ve skleněné ampuli 1 hodinu při 20 °C. Reakční směs byla zředěna 20 ml 1,1,2-trichIortrifluorethanu, vytřepána vodou a vysušena bezvodým síranem hořečnatým. Rektifikaci byl získán perfluor-4-methyl-2-pentendinitril ve výtěžku 0,61 g.A mixture of 1 g of triethylamine, 5 g of trifluoroacrylonitrile and 20 ml of acetonitrile was shaken in a glass vial for 1 hour at 20 ° C. The reaction mixture was diluted with 20 mL of 1,1,2-trichlorotrifluoroethane, shaken with water and dried over anhydrous magnesium sulfate. Rectification gave perfluoro-4-methyl-2-pentendinitrile in a yield of 0.61 g.
Příklad 7Example 7
Směs 1 g triethanolaminu, 5 g trifluorakrylonitrilu a 20 ml acetonitrilu byla třepána ve skleněné ampuli při teplotě 20 °C po 1 hodinu. Reakční směs byla zředěna 20 ml 1,1,2-trichlortrifluorethanu, promyta vodou a vysušena bezvodým síranem hořečnatým. Po oddestilování rozpouštědla byl rektifikaci získán perfluor-4-methyl-2-pentendinitril ve výtěžku 0,81 g.A mixture of 1 g of triethanolamine, 5 g of trifluoroacrylonitrile and 20 ml of acetonitrile was shaken in a glass vial at 20 ° C for 1 hour. The reaction mixture was diluted with 20 mL of 1,1,2-trichlorotrifluoroethane, washed with water and dried over anhydrous magnesium sulfate. After distillation of the solvent, perfluoro-4-methyl-2-pentendinitrile was obtained in a yield of 0.81 g.
Příklad 8Example 8
Směs 1 g fluoridu draselného, 5 g trifluorakrylonitrilu a 15 ml hexamethyltriamidofosfátu byla třepána při 30—40 °C po 2,5 hodiny. Reakční směs byla destilována za tlaku 13,3 kPa a produkt byl zachycen v jímadle chlazeném suchým ledem. Rektifikaci byl získán perfluor-4-methyl-2-pentendinitril ve výtěžku 0,93 g.A mixture of 1 g of potassium fluoride, 5 g of trifluoroacrylonitrile and 15 ml of hexamethyltriamidophosphate was shaken at 30-40 ° C for 2.5 hours. The reaction mixture was distilled at 50 psi and the product was collected in a dry ice cooled receiver. Rectification gave perfluoro-4-methyl-2-pentendinitrile in a yield of 0.93 g.
Příklad 9Example 9
Směs 1 g fluoridu česného, 5 g trifluorakrylonitrilu a 20 ml dimethylformamidu byla třepána ve skleněné ampuli při 60 °C po 2 hodiny. Reakční směs byla po odfiltrování pevné fáze destilována a byl získán perfluor-4-methyl-2-pentendinitril ve výtěžku 0,07 g.A mixture of 1 g cesium fluoride, 5 g trifluoroacrylonitrile and 20 ml dimethylformamide was shaken in a glass vial at 60 ° C for 2 hours. The reaction mixture was distilled off after solids were filtered off to give perfluoro-4-methyl-2-pentendinitrile in a yield of 0.07 g.
Příklad 10Example 10
Směs 1,3 g tetraethylamoniumfluoridu, 5 g trifluorakrylonitrilu, 15 ml dimethyletheru a 5 ml nitrobenzenu byla třepána ve skleněné ampuli při 40—50 C po 2 hodiny. Reakční směs byla zředěna 15 ml 1,1,2-trichlortrifluorethanu, promyta vodou a vysušena bezvodým síranem hořečnatým. Rektifikaci byl získán perfluor-4-methyl-2-pentendinitril ve výtěžku 1,46 g.A mixture of 1.3 g of tetraethylammonium fluoride, 5 g of trifluoroacrylonitrile, 15 ml of dimethyl ether and 5 ml of nitrobenzene was shaken in a glass vial at 40-50 ° C for 2 hours. The reaction mixture was diluted with 15 mL of 1,1,2-trichlorotrifluoroethane, washed with water and dried over anhydrous magnesium sulfate. Rectification gave perfluoro-4-methyl-2-pentendinitrile in a yield of 1.46 g.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS151479A CS204582B1 (en) | 1979-03-07 | 1979-03-07 | Process for preparing perfluor-4-methyl-2-pentendinitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS151479A CS204582B1 (en) | 1979-03-07 | 1979-03-07 | Process for preparing perfluor-4-methyl-2-pentendinitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS204582B1 true CS204582B1 (en) | 1981-04-30 |
Family
ID=5349720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS151479A CS204582B1 (en) | 1979-03-07 | 1979-03-07 | Process for preparing perfluor-4-methyl-2-pentendinitrile |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS204582B1 (en) |
-
1979
- 1979-03-07 CS CS151479A patent/CS204582B1/en unknown
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